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Title: Lithium aluminum–layered double hydroxide chlorides (LDH): Formation enthalpies and energetics for lithium ion capture

Abstract

Abstract Layered aluminum double hydroxide chloride sorbents, LiCl∙Al 2 ( OH ) 6 . nH 2 O, Li‐ LDH , have shown promising application in selective Li extraction from geothermal brines. Maintaining LiCl uptake capacity and retaining a long cycle life are critical to widespread application of sorbent materials. To elucidate the energetics of Li capture, enthalpies of LDH with different Li content have been measured by acid solution calorimetry. The formation enthalpies generally become less exothermic as the Li content increases, which indicates that Li intercalation destabilizes the structure, and the enthalpies seem to approach a limit after the Li content x = 2Li/Al exceeds 1. To improve stability, metal doping of the aluminum LDH structure with iron was performed. Introduction of a metal with greater electron density but a similar ionic radius was postulated to improve the stability of the LDH crystal structure. The calorimetric results from Fe‐doped LDH samples corroborate this as they are more exothermic than LDH ‐lacking Fe. This suggests that Fe doping is an effective way to stabilize the LDH phase.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [2]; ORCiD logo [2];  [4];  [4];  [5]; ORCiD logo [3];  [4]; ORCiD logo [1]
  1. Univ. of California, Davis, CA (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); The Univ. of Tennessee, Knoxville, TN (United States)
  4. Rutgers Univ., Piscataway, NJ (United States)
  5. Alger Alternative Energy, LLC, Brawley, CA (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1560502
Alternate Identifier(s):
OSTI ID: 1787126
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Ceramic Society
Additional Journal Information:
Journal Volume: 102; Journal Issue: 5; Journal ID: ISSN 0002-7820
Publisher:
American Ceramic Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; heat capacity; high‐temperature calorimetry; lithium aluminum hydroxide chloride; lithium extraction; sorbents

Citation Formats

Wu, Lili, Li, Ling, Evans, Samuel F., Eskander, Tessa A., Moyer, Bruce A., Hu, Zhichao, Antonick, Paul J., Harrison, Stephen, Paranthaman, M. Parans, Riman, Richard, and Navrotsky, Alexandra. Lithium aluminum–layered double hydroxide chlorides (LDH): Formation enthalpies and energetics for lithium ion capture. United States: N. p., 2018. Web. doi:10.1111/jace.16150.
Wu, Lili, Li, Ling, Evans, Samuel F., Eskander, Tessa A., Moyer, Bruce A., Hu, Zhichao, Antonick, Paul J., Harrison, Stephen, Paranthaman, M. Parans, Riman, Richard, & Navrotsky, Alexandra. Lithium aluminum–layered double hydroxide chlorides (LDH): Formation enthalpies and energetics for lithium ion capture. United States. https://doi.org/10.1111/jace.16150
Wu, Lili, Li, Ling, Evans, Samuel F., Eskander, Tessa A., Moyer, Bruce A., Hu, Zhichao, Antonick, Paul J., Harrison, Stephen, Paranthaman, M. Parans, Riman, Richard, and Navrotsky, Alexandra. Sat . "Lithium aluminum–layered double hydroxide chlorides (LDH): Formation enthalpies and energetics for lithium ion capture". United States. https://doi.org/10.1111/jace.16150. https://www.osti.gov/servlets/purl/1560502.
@article{osti_1560502,
title = {Lithium aluminum–layered double hydroxide chlorides (LDH): Formation enthalpies and energetics for lithium ion capture},
author = {Wu, Lili and Li, Ling and Evans, Samuel F. and Eskander, Tessa A. and Moyer, Bruce A. and Hu, Zhichao and Antonick, Paul J. and Harrison, Stephen and Paranthaman, M. Parans and Riman, Richard and Navrotsky, Alexandra},
abstractNote = {Abstract Layered aluminum double hydroxide chloride sorbents, LiCl∙Al 2 ( OH ) 6 . nH 2 O, Li‐ LDH , have shown promising application in selective Li extraction from geothermal brines. Maintaining LiCl uptake capacity and retaining a long cycle life are critical to widespread application of sorbent materials. To elucidate the energetics of Li capture, enthalpies of LDH with different Li content have been measured by acid solution calorimetry. The formation enthalpies generally become less exothermic as the Li content increases, which indicates that Li intercalation destabilizes the structure, and the enthalpies seem to approach a limit after the Li content x = 2Li/Al exceeds 1. To improve stability, metal doping of the aluminum LDH structure with iron was performed. Introduction of a metal with greater electron density but a similar ionic radius was postulated to improve the stability of the LDH crystal structure. The calorimetric results from Fe‐doped LDH samples corroborate this as they are more exothermic than LDH ‐lacking Fe. This suggests that Fe doping is an effective way to stabilize the LDH phase.},
doi = {10.1111/jace.16150},
journal = {Journal of the American Ceramic Society},
number = 5,
volume = 102,
place = {United States},
year = {Sat Oct 13 00:00:00 EDT 2018},
month = {Sat Oct 13 00:00:00 EDT 2018}
}

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Cited by: 21 works
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Figures / Tables:

Table 1 Table 1: Sample composition, TG weight loss at 700°C, enthalpy of solution (ΔHsol) in 5N HCl and the formation enthalpies of LDH (ΔHf) by LiCl reacted with gibbsite and goethite.

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.